This Thesis describes the synthesis and characterisation of titanium hydrazido(2-) complexes and their reactivity towards unsaturated molecules. Exploration of the bonding in titanium hydrazido(2-) complexes is performed through structural and computational studies. <strong>Chapter 1</strong> introduces current Group 4 hydrazido chemistry and describes its relevance with comparison to Group 4 imido and mid/late metal hydrazido examples. <strong>Chapter 2</strong> describes the synthesis and characterisation of new titanium hydrazido(2-) half-sandwich complexes. A general route to new titanium hydrazido(2-) chemistry is described and suppression of dimerisation pathways common to Group 4 alkyl hydrazido(2-) chemistry is investigated. <strong>Chapter 3</strong> describes the synthesis, bonding and preliminary reaction chemistry of a new titanium hydrazido(2-) sandwich complex. Through structural and computational techniques, the bonding in the sandwich complex Cp<sub>2</sub>Ti(NNPh<sub>2</sub>)(py) (14) is explored and the implications to the reactivity of this complex considered. <strong>Chapter 4</strong> describes the synthesis of new titanium hydrazido(2-) synthons which is extended to the synthesis of new titanium hydrazido(2-) complexes with diamide-amine type ligands. The bonding of the hydrazido(2-) ligand is explored through structural and computational study of these complexes. <strong>Chapter 5</strong> describes the novel reaction chemistry of a diamide-pyridyl titanium hydrazido(2-) complex Ti(N<sub>2</sub>N<sup>py</sup>)(NNPh<sub>2</sub>)(py) (23). Novel reactivity of both the Ti=N<sub>α</sub> and N<sub>α</sub>-N<sub>β</sub> bonds is presented with the mechanisms of some of these transformations probed by density functional theory (DFT) calculations. <strong>Chapter 6</strong> presents full experimental procedures and characterising data for the new complexes reported. <strong>CD Appendix</strong> contains .cif files for all new crystallographically characterised complexes described.
| Identifer | oai:union.ndltd.org:bl.uk/oai:ethos.bl.uk:510221 |
| Date | January 2009 |
| Creators | Selby, Jonathan D. |
| Contributors | Mountford, Philip |
| Publisher | University of Oxford |
| Source Sets | Ethos UK |
| Detected Language | English |
| Type | Electronic Thesis or Dissertation |
| Source | http://ora.ox.ac.uk/objects/uuid:afee94b7-7cd7-437c-8c31-1cba8a145720 |
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